Halogenated extreme pressure lubricant



Patented Aug. 10, 1943 HALOGENATED EXTREME PRESSURE LUBRICANT Norman D. Williams, Chicago, 111., assignor to The Pure Oil Company, Chicago, 111., a corporation of Ohio No Drawing. Original application October 19, 1938, Serial No. 235,775, now Patent No. 2,235,860, dated March 25, 1941. Divided and this application February 5, 1941, Serial No.

This invention relates to lubricants and to the method of preparing and using the same, and is more particularly concerned with lubricants having extreme pressure characteristics.

This application is a division of my co-pending application, Serial No. 235,775 filed October 19, 1938, entitled Halogenated E. P. lubricants,

now Patent No. 2,235,860.

It is well known that mineral lubricating oils can be improved by adding thereto halogenated aromatic hydrocarbons and compounds in which hydrogen in the aromatic nucleus is substituted by chlorine. Many halogenated aliphatic hydrocarbons and compounds in general have been found to be unsatisfactory because such pounds hydrolyze readily in contact with water forming acid which oorrodes the metal surfaces.

I have discovered that certain chlorinated esters and ketones, where the chlorine is attached to a carbon which is located between or protected by non-acidic, stable, aromatic or other carbocyclic nuclei, are not only not corrosive but are more active than the halogenated aromatics. Such compounds have the ability to impart to mineral lubricating oils increased oiliness, film strength and extreme pressure characteristics.

Thecompounds which I have discovered to be suitable are those of the type RCn-COOCn-R' and RC fl CO''C flR in which R and R are non-acidic, stable, aromatic or other carbocyclic nuclei either the same or difierent, CO0 is the characteristic group found in esters, CO is the bivalent ketone group found in ketones, C represents an aliphatic carbon radical either saturated or unsaturated having any number (n) of carbon atoms and which compounds have halogen united to one or more aliphatic carbon atoms which are linked between the carbocyclic nuclei.

These compounds are similar tothose disclosed in the co-pending application of William A. Whittier, Ser. No. 180,487, but from thecompounds therein disclosed by containing the characteristic COO ester group or CO ketone r pr Examples of compounds which are suitable for use are dichlorphenyl ethyl cinnamate, tetra-' chlorcinnamyl cinnamate, dichlor cinnamyl acetophenone, tetrachlor dibenzylidene acetone and octachlor dicinnamylideneacetone,

2,8-dichlor phenylacetal-acetophenone, 2,3 dichlor phenylacetal-benzalacetone, 1,2,3,4, tetra -dichlor benzalacetophenone, 1,2-dichlor benzalacetone,

chlor cinnamylacetophenone, 1,2,3,4,.tetrachlor cinnamyl-benzalacetone, d1 chlor benzyl cinnamate and dichlor benzyl a-phenyl cinnamate.

4 Claims. (01.252-54) The halogen may be added directly to the carbon in those compounds which are unsaturated or may replace the hydrogen in those compounds which are saturated. In the case of unsaturated compounds, halogen may be linked to the carbon by direct addition and by substitution of the hydrogen. Generally speaking, the greater the number of chlorine atoms linked to the carbon, the greater is the effectiveness of the compound as an E. If. agent.

To illustrate moreclearly the nature of he compounds with which this invention is concerned, the following graphic formulae are shown:

illicit l. h i i Diohlorphenylethyl cinnamate Eiiiiiiii 131 $1 61 All J31 (:1 $1 111 octachlordicinnamylidnne acetone E J J E Z-i 01 I a t; h

Tetraehlor derivative of para para dibenzylidene acetone CHxO I OCH! t1 1 Y A;

Tetrachlor dianisylideno acetone 4 to 200 F. for 15 minutes. During this time only a slight darkening of the oil occurs. The temperature is then slowly increased to 275 F. in order to drive on any remaining phosphorous oxychlorlde. A black sludge forms in the amount of approidmately 25%. j 5% of'the oil, after it has been decanted from the sludge, is blended with 95% of lubricating oil having the following characteristics: 1

Gravity, A. P. I 21-. 23 Flash, F 530-540 Fire, F 000-010 Viscosity, Saybolt at 210 F 155-165 Pour, F -25 I have found that when small quantities of halogenated compounds of the nature of those 104 above described are incorporated in a blend of mineral lubricating oil with a sulfurized and phosphorized fatty 011 base such as that disclosed in the application of Whittier et al., Ser. No.

55,200, the extreme pressure characteristicsof 15 such lubricants canbe materially improved. A.

number of tests have been made on straight lubricants blended with halogenated compounds of the nature of those above set forth and on lubricants blended with sulfurized and phos-, 2o

phorized base together with'halogenated compounds, the results of which are given in Table III. In these tests thestraight mineral oil used was a blend to approximately S. A. E. 90 viscosity In those tests in which a mineral oil was blended with sulfurized-phosphorized base and/0r chlorinated compound, the lubricating oil before blending had the following characteristics:

The sulfurized-phosphorized base was made in the following manner: A homogeneous mixture of 570 pounds of Gulf Coast pale oil having a Saybolt Universal viscosity at 100 F. of 200 seconds and a pour point of --'-20 to 25 F. and 55 pounds of sulfur chloride was prepared in a cold state. This mixture was added to 9,581 pounds of prime lard oil contained in an enclosed steam jacketed kettle. The mixture was heated to 275 F. while being vigorously agitated. At

this point the steam was shut ofi and 814 pounds of flowers of sulfur were sifted into the contents of the kettle over a period of approximately two hours, The contents of the'kettle were vigorously agitated during this entire period. At the end of the two-hour period the temperature had dropped to 265 F. The steam was again turned on and the contents of. the kettle heated to approximately 300 F. when the steam was turned off. Agitation was continued for a period of approximately 7 /2 hours after the addition of the sulfur. During this period the temperature rose from 300 to 344 F. during the first three hours, indicating that an exothermic reaction was taking place, The temperature during the 'l /z-hour period was not permitted to drop below 320 F. and it was found that it was unnecessary to use any further heat to maintain this temperature after-the mixture had been initially heated to 300F.

The sulfurized material was then cooled to a temperature of 220 to 230 F. by circulating the material through cooling coils and back to the kettle. When this temperature had been reached, 44 pounds of phosphorous sesqui-sulfide' was added slowly over a period of hour of continu-. ous agitation. The steam was again turned on at such times as was necessary to maintain the temperature at 220 to 230 F. After the addition ohlorho.

lubricant! named "Sui. 0t lulfurll and phoaphorizod fatty oil.

Faileatoho dstartingload.

This oil was blended with sulfurized phosphorized base in the proportion of 82% of oil "to 18% of base.

of phosphorous sesqui-sulfide, agitation was con- Table II tinued for a period of approximately five hours A.P. I, gravity 18- 20. while the temperature was maintained at 220 m h F 7 380-400 to 230 F. At the end of this period the conn- "F 430-450 45 tents of the kettle were immediately cooled to ya. at 130 F. (Say. Univ.) 460-500 130 F. by circulation through the exteriorly 10- Via. at 210 F. (Say. Univ.) 90- 95 cated cooling coils and pumped to storage. Pour point, F 0 The following is a table of results obtained: Table III v Pen, Timkeuteat Halogenated compound added gg fifigg Beam B P M i 091. Md Presure L L0- Mimi-01 'o11 '12 "1, 1'5-50 Dkdflorphenylethylclnnsmate 5.0 'ml :3 251328 a? Do 5.5 m :15 1.25 -.c.o 510 5.0 do 00 51,500 000 1.25 .----do 000 5.0 -.do 80 00,250 405 1.2 do 325 0.0 05 000 5.0 0 00 33,750 540 2.5 ..do 310 2.0 Mineral on 51 15,750 2.0 n 50 15,500 00 5.0 do 320 10.0 n 350 phos. base blend" are composed of 82% mineral oil and 18% by volume The tests were madeon the machine recommended as a tentative standardvby the Society of Automotive Engineers for testing extreme Presthe chlorinated compounds when blended in,

small quantities with straight mineral oil tested only approximately 16,000 lbs. per sq. in. on the Timken machine and 90 lbs. on the S. A. E. ma-

chine. The E. P. characteristics of a phosphorized or a sulfurized-phosphorized lubricant as determined by the Timken machine, are not appreciably altered by addition of the halogen compound while greatly increasing the film strength and E. P. characteristics 01 the lubricant as measured by the S. A. E. machine. The Timken test' results of the sulfurized-phosphorized lubricant blended with a chlorine compound are the same asthe unblended material within the limit of accuracy of the testing machine. Corrosion tests made in the presence of water indicate that the halogenated compound may be introduced into the lubricant without rendering it corrosive.

Although I do not wish to be limited to the addition of any particular amount of the halogenated compound to the lubricant, I prefer to use from approximately 1% to 10% by volumle in connection with lubricants to be used where E. P. characteristics are important. Where the compound is added to improve the oiliness and film strength, as for example, in motor oil, the amount added may range from a fraction of 1% to approximately 5%. The upper limit of has been fixed only because with the methods of testing now available, it has been found that maximum results can be obtained-by adding this amount. There is no reason, however, why quantities in excess of 10% may not be used.

Instead of adding the halogenated compound directly to the oil, it may be separately fed into the particular mechanism to be lubricated and mixed in situ with the lubricating oil.

It has also been found that materials within the scope of this invention containing a phosphorized or suliurized and phosphorized lubricant and chlorinated ester or ketone oi the class previously described, are excellent cutting fluids and are also well adapted to be used in drawing, grinding and burnishing operations. They may be used straight, blended with mineral oil and/or emulsified. with water.

What I claim is:

l. A lubricant comprising'mineral lubricating oil and a compound selected from the group of halogenated ketones of the type RCnCOCnR' and halogenated esters oi the type RCnCOOCnR' in which R and R are non-acidic, stable, carbo cyclic radicals either the same or different, CO and COO are the characteristic ketone and ester groups, C is an aliphatic chain having any number (n) of carbon atoms, said compound containing halogen linked to carbon in only one aliphatic chain.

2. A lubricant in accordance with claim 1 m which the compound is dichlorphenyl ethyl cinnamate.

3. A lubricant in accordance with claim 1 in which the said compound is present in amount or 1 to 10% by volume.

4. A lubricant in accordance with claim 1 to which has been added sulfurized and phosphorized fatty material.

NORMAN D. WILLIAMS. 

